US3920670A - Process for hydrolysis of nitriles - Google Patents
Process for hydrolysis of nitriles Download PDFInfo
- Publication number
- US3920670A US3920670A US404966A US40496673A US3920670A US 3920670 A US3920670 A US 3920670A US 404966 A US404966 A US 404966A US 40496673 A US40496673 A US 40496673A US 3920670 A US3920670 A US 3920670A
- Authority
- US
- United States
- Prior art keywords
- acid
- nitrile
- aromatic
- catalyst
- hydrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 28
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 17
- 239000003377 acid catalyst Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 22
- -1 heterocyclic nitrile Chemical class 0.000 claims abstract description 21
- 150000001408 amides Chemical class 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 38
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 10
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical group N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000002790 naphthalenes Chemical class 0.000 claims description 5
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical group N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical group N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 4
- ZBFVJRBOKDTSMO-UHFFFAOYSA-N naphthalene-2,6-dicarbonitrile Chemical group C1=C(C#N)C=CC2=CC(C#N)=CC=C21 ZBFVJRBOKDTSMO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 12
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920006391 phthalonitrile polymer Polymers 0.000 description 2
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 description 1
- FVUKYCZRWSQGAS-UHFFFAOYSA-N 3-carbamoylbenzoic acid Chemical compound NC(=O)C1=CC=CC(C(O)=O)=C1 FVUKYCZRWSQGAS-UHFFFAOYSA-N 0.000 description 1
- JMHSCWJIDIKGNZ-UHFFFAOYSA-N 4-carbamoylbenzoic acid Chemical compound NC(=O)C1=CC=C(C(O)=O)C=C1 JMHSCWJIDIKGNZ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- SGLGUTWNGVJXPP-UHFFFAOYSA-N benzene-1,3,5-tricarbonitrile Chemical compound N#CC1=CC(C#N)=CC(C#N)=C1 SGLGUTWNGVJXPP-UHFFFAOYSA-N 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- NNHXOKPHDUDDAK-UHFFFAOYSA-N naphthalene-2,7-dicarbonitrile Chemical compound C1=CC(C#N)=CC2=CC(C#N)=CC=C21 NNHXOKPHDUDDAK-UHFFFAOYSA-N 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920005554 polynitrile Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
Definitions
- ABSTRACT A process for the catalytic acid hydrolysis of an aro matic or heterocyclic nitrile to acid by feeding an aqueous solution of the nitrile and acid catalyst to a reflux reactor held at a temperature and pressure to maintain liquid reflux conditions whereby hydrolysis of 'nitriie occurs and the ammonium salt of the acid catalyst which forms pyrolyzes to amide, distilling off vapors of said catalyst and the amide of said catalyst. and separating from said reactor aromatic acid or heterocyclic acid product in high purity.
- ammonium salt in equilibrium with free aromatic acid and ammonium acetate:
- the process is applicable to a wide variety of aromatic and heterocyclic monoand polynitriles such as benzonitrile. toluonitrile. phthalonitrile, isophthalonitrile, terephthalonitrile, 1,3,5-tricyanobenzene, 2,6- dicyanonaphthalene, nicotinonitrile, and other heteroaromatic nitrile compounds of the benzene and naphthalene series; e.g., the benzo-, toluoand phthalonitriles, most preferably iso and terephthalonitriles and 2,6- or 2,7-dicyanonaphthalene.
- the acid catalyst used in the process will be any water soluble acid whose ammonium salt may be readily dehydrated under the reflux conditions used in the process. Also the acid catalyst should have an appreciable rate of hydrolysis and its amide should have a vapor pressure greater than the aromatic acid or heterocyclic acid being formed. Most preferably, acetic acid will be the acid used, but other preferred operable acids include lower aliphatic acids of 1 to 4 carbon atoms and benzoic acid.
- EXAMPLE 1 A slurry of terephthalonitrile (1 mole), acetic acid (5 moles) and water (500 ml.) was hydrolyzed at 250C. for 3 hours. A constant volume single plate distillation was then started using a feed of acetic acidzwater (1:5 molar ratio) at 250C. The condensed distillate was concentrated and acetamide isolated by filtration. From 12 l. of distillate 1.8 moles of acetamide were removed of theory), and from filtration of the reactor slurry at [00C, terephthalic acid was isolated (161 g. 0.97 moles) containing 0.01% N as terephthalamic acid.
- EXAMPLE 3 In a manner similar to Examples 1 and 2, 2,6- dicyanonaphthalene, (0.50 moles) in ml. of water and hydrolyzed at 280C. for 10 hours. Subsequently, a constant volume single plate distillation using a feed of acetic acid:water (10:1 mole ratio) at 250C. yielded acetamide and 2,6-napthalene dicarboxylic acid in 85% yield containing 0.02% N as amide impurity.
- EXAMPLE 4 In the manner of Example 3, nicotinonitrile was allowed to react with propionic acid. and after hydrolysis and distillation, nicotinic acid was isolated in high yield.
- a process for the catalytic acid hydrolysis of an aromatic or heterocyclic nitrile to the corresponding acid which comprises heating an aqueous solution of a nitrile from the group consisting of nitriles of the benzene. naphthalene and heterocyclic series and an acid catalyst which has an appreciable rate of hydrolysis and whose amide has a vapor pressure greater than the nitrile derived acid product, said heating being carried out in a reactor held at a temperature and pressure to maintain liquid reflux conditions, whereby hydrolysis of the nitrile occurs and the ammonium salt of the acid catalyst which forms is pyrolyzed to amide, distilling off vapors of said acid catalyst and the amide, and separating from said reactor the corresponding aromatic or heterocyclic acid products in high purity.
- nitrile is an aromatic nitrile of the benzene or naphthalene series and the acid catalyst is acetic acid.
- nitrile is a heterocyclic nitrile containing 4 to 5 carbon atoms and the acid catalyst is acetic acid.
- a process for the catalytic acid hydrolysis of an aromatic nitrile of the benzene or naphthalene series which comprises refluxing under autogenous pressure in a reflux reactor, an aqueous solution of the nitrile and as catalyst a lower aliphatic acid of l to 4 carbon atoms at a temperature of to 330C. whereby hydrolysis of the nitrile occurs and the ammonium salt of the acid catalyst which forms is dehydrated by pyrolysis to the corresponding amide, distilling off vapors of said acid catalyst and said amide. and separating from said reactor the corresponding aromatic acid product in high purity.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US404966A US3920670A (en) | 1973-10-10 | 1973-10-10 | Process for hydrolysis of nitriles |
| IT25792/74A IT1017768B (it) | 1973-10-10 | 1974-07-31 | Procedimento per l idrolisi di nitrili |
| GB3454474A GB1433468A (en) | 1973-10-10 | 1974-08-06 | Process for hydrolysis of nitriles |
| DE2438263A DE2438263A1 (de) | 1973-10-10 | 1974-08-08 | Verfahren zur katalytischen saeurehydrolyse von aromatischen oder heterocyclischen nitrilen zu den entsprechenden saeuren |
| JP49092431A JPS5064212A (enrdf_load_stackoverflow) | 1973-10-10 | 1974-08-14 | |
| NL7411438A NL7411438A (nl) | 1973-10-10 | 1974-08-28 | Werkwijze voor het katalytisch hydrolyseren uur van een aromatisch of heterocyclisch l. |
| SU7402065456A SU569279A3 (ru) | 1973-10-10 | 1974-09-08 | Способ получени кислот ароматического р да |
| CA208,954A CA1034130A (en) | 1973-10-10 | 1974-09-11 | Process for hydrolysis of nitriles |
| IL45730A IL45730A (en) | 1973-10-10 | 1974-09-24 | Process for hydrolysis of nitriles |
| FR7433925A FR2247436B1 (enrdf_load_stackoverflow) | 1973-10-10 | 1974-10-09 | |
| BE149387A BE820905A (fr) | 1973-10-10 | 1974-10-10 | Procede d'hydrolyse de nitriles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US404966A US3920670A (en) | 1973-10-10 | 1973-10-10 | Process for hydrolysis of nitriles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3920670A true US3920670A (en) | 1975-11-18 |
Family
ID=23601759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US404966A Expired - Lifetime US3920670A (en) | 1973-10-10 | 1973-10-10 | Process for hydrolysis of nitriles |
Country Status (11)
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116967A (en) * | 1976-10-07 | 1978-09-26 | The Lummus Company | Production of carboxylic acids from nitriles |
| EP0731079A3 (enrdf_load_stackoverflow) * | 1995-03-08 | 1996-10-16 | Daicel Chem | |
| US6100427A (en) * | 1997-10-30 | 2000-08-08 | Catalytic Distillation Technologies | Production of amides and/or acids from nitriles |
| US20070161820A1 (en) * | 2006-01-12 | 2007-07-12 | Sanders David J | Simultaneous recovery and continuous extraction of substantially pure carboxylic acids and ammonium salts from acid hydrolysis reaction mixtures |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3614019A1 (de) | 1986-04-25 | 1987-11-05 | Degussa | Verfahren zur herstellung grobkristalliner nicotinsaeure hoher reinheit |
| CN101550047B (zh) * | 2008-04-03 | 2013-06-05 | 上海药明康德新药开发有限公司 | 一种脱叔烷基胺的方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3146238A (en) * | 1964-08-25 | Process of preparing pyridine carboxyl | ||
| US3155673A (en) * | 1964-11-03 | Process for preparing vitamin b | ||
| US3781343A (en) * | 1973-04-12 | 1973-12-25 | Sun Research Development | Hydrolysis of aromatic dinitriles |
-
1973
- 1973-10-10 US US404966A patent/US3920670A/en not_active Expired - Lifetime
-
1974
- 1974-07-31 IT IT25792/74A patent/IT1017768B/it active
- 1974-08-06 GB GB3454474A patent/GB1433468A/en not_active Expired
- 1974-08-08 DE DE2438263A patent/DE2438263A1/de not_active Withdrawn
- 1974-08-14 JP JP49092431A patent/JPS5064212A/ja active Pending
- 1974-08-28 NL NL7411438A patent/NL7411438A/xx not_active Application Discontinuation
- 1974-09-08 SU SU7402065456A patent/SU569279A3/ru active
- 1974-09-11 CA CA208,954A patent/CA1034130A/en not_active Expired
- 1974-09-24 IL IL45730A patent/IL45730A/xx unknown
- 1974-10-09 FR FR7433925A patent/FR2247436B1/fr not_active Expired
- 1974-10-10 BE BE149387A patent/BE820905A/xx unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3146238A (en) * | 1964-08-25 | Process of preparing pyridine carboxyl | ||
| US3155673A (en) * | 1964-11-03 | Process for preparing vitamin b | ||
| US3781343A (en) * | 1973-04-12 | 1973-12-25 | Sun Research Development | Hydrolysis of aromatic dinitriles |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116967A (en) * | 1976-10-07 | 1978-09-26 | The Lummus Company | Production of carboxylic acids from nitriles |
| EP0731079A3 (enrdf_load_stackoverflow) * | 1995-03-08 | 1996-10-16 | Daicel Chem | |
| US5763652A (en) * | 1995-03-08 | 1998-06-09 | Daicel Chemical Industries, Ltd. | Process for producing a carboxylic acid |
| CN1073078C (zh) * | 1995-03-08 | 2001-10-17 | 大赛璐化学工业株式会社 | 制备羧酸的方法 |
| US6100427A (en) * | 1997-10-30 | 2000-08-08 | Catalytic Distillation Technologies | Production of amides and/or acids from nitriles |
| US20070161820A1 (en) * | 2006-01-12 | 2007-07-12 | Sanders David J | Simultaneous recovery and continuous extraction of substantially pure carboxylic acids and ammonium salts from acid hydrolysis reaction mixtures |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2247436B1 (enrdf_load_stackoverflow) | 1978-06-09 |
| FR2247436A1 (enrdf_load_stackoverflow) | 1975-05-09 |
| JPS5064212A (enrdf_load_stackoverflow) | 1975-05-31 |
| IT1017768B (it) | 1977-08-10 |
| CA1034130A (en) | 1978-07-04 |
| NL7411438A (nl) | 1975-04-14 |
| BE820905A (fr) | 1975-04-10 |
| IL45730A (en) | 1979-11-30 |
| GB1433468A (en) | 1976-04-28 |
| IL45730A0 (en) | 1974-11-29 |
| SU569279A3 (ru) | 1977-08-15 |
| DE2438263A1 (de) | 1975-04-17 |
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